A di‑iron(III) μ-oxido complex as catalyst precursor in the oxidation of alkanes and alkenes
(2022) In Journal of Inorganic Biochemistry 231.- Abstract
The oxido-bridged diiron(III) complex [Fe2(μ-O)(μ-OAc)(DPEAMP)2](OCH3) (1), based on a new unsymmetrical ligand with an N4O donor set, viz. [2-((bis(pyridin-2-ylmethyl)amino)methyl)-6-((ethylamino)methyl)-4-methylphenol (HDPEAMP)], has been prepared and characterized by spectroscopic methods and X-ray crystallography. The crystal structure of the complex reveals that each Fe(III) ion is coordinated by three nitrogen and three oxygen donors, two of which are the bridging oxido and acetate ligands. Employing H2O2 as a terminal oxidant, 1 is capable of oxidizing a number of alkanes and alkenes with high activity. The catalytic oxidation of 1,2-dimethylcyclohexane results in... (More)
The oxido-bridged diiron(III) complex [Fe2(μ-O)(μ-OAc)(DPEAMP)2](OCH3) (1), based on a new unsymmetrical ligand with an N4O donor set, viz. [2-((bis(pyridin-2-ylmethyl)amino)methyl)-6-((ethylamino)methyl)-4-methylphenol (HDPEAMP)], has been prepared and characterized by spectroscopic methods and X-ray crystallography. The crystal structure of the complex reveals that each Fe(III) ion is coordinated by three nitrogen and three oxygen donors, two of which are the bridging oxido and acetate ligands. Employing H2O2 as a terminal oxidant, 1 is capable of oxidizing a number of alkanes and alkenes with high activity. The catalytic oxidation of 1,2-dimethylcyclohexane results in excellent retention of configuration. Monitoring of the reaction of 1 with H2O2 and acetic acid in the absence of substrate, using low-temperature UV–Vis spectroscopy, suggests the in situ formation of a transient Fe(III)2-peroxido species. While the selectivity and nature of oxidation products implicate a high-valent iron-oxido complex as a key intermediate, the low alcohol/ketone ratios suggest a simultaneous radical-based process.
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- author
- Das, Biswanath LU ; Al-Hunaiti, Afnan ; Carey, Akina ; Lidin, Sven LU ; Demeshko, Serhiy ; Repo, Timo and Nordlander, Ebbe LU
- organization
- publishing date
- 2022
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Catalysis, Epoxidation, Hydroxylation, Iron, Metal-oxido complex, Peroxide complex
- in
- Journal of Inorganic Biochemistry
- volume
- 231
- article number
- 111769
- publisher
- Elsevier
- external identifiers
-
- pmid:35287038
- scopus:85126777903
- ISSN
- 0162-0134
- DOI
- 10.1016/j.jinorgbio.2022.111769
- language
- English
- LU publication?
- yes
- id
- bc446e1b-d993-4bba-9eb9-7ff0864fbd3d
- date added to LUP
- 2022-04-19 12:41:02
- date last changed
- 2024-09-08 02:41:31
@article{bc446e1b-d993-4bba-9eb9-7ff0864fbd3d, abstract = {{<p>The oxido-bridged diiron(III) complex [Fe<sub>2</sub>(μ-O)(μ-OAc)(DPEAMP)<sub>2</sub>](OCH<sub>3</sub>) (1), based on a new unsymmetrical ligand with an N<sub>4</sub>O donor set, viz. [2-((bis(pyridin-2-ylmethyl)amino)methyl)-6-((ethylamino)methyl)-4-methylphenol (HDPEAMP)], has been prepared and characterized by spectroscopic methods and X-ray crystallography. The crystal structure of the complex reveals that each Fe(III) ion is coordinated by three nitrogen and three oxygen donors, two of which are the bridging oxido and acetate ligands. Employing H<sub>2</sub>O<sub>2</sub> as a terminal oxidant, 1 is capable of oxidizing a number of alkanes and alkenes with high activity. The catalytic oxidation of 1,2-dimethylcyclohexane results in excellent retention of configuration. Monitoring of the reaction of 1 with H<sub>2</sub>O<sub>2</sub> and acetic acid in the absence of substrate, using low-temperature UV–Vis spectroscopy, suggests the in situ formation of a transient Fe(III)<sub>2</sub>-peroxido species. While the selectivity and nature of oxidation products implicate a high-valent iron-oxido complex as a key intermediate, the low alcohol/ketone ratios suggest a simultaneous radical-based process.</p>}}, author = {{Das, Biswanath and Al-Hunaiti, Afnan and Carey, Akina and Lidin, Sven and Demeshko, Serhiy and Repo, Timo and Nordlander, Ebbe}}, issn = {{0162-0134}}, keywords = {{Catalysis; Epoxidation; Hydroxylation; Iron; Metal-oxido complex; Peroxide complex}}, language = {{eng}}, publisher = {{Elsevier}}, series = {{Journal of Inorganic Biochemistry}}, title = {{A di‑iron(III) μ-oxido complex as catalyst precursor in the oxidation of alkanes and alkenes}}, url = {{http://dx.doi.org/10.1016/j.jinorgbio.2022.111769}}, doi = {{10.1016/j.jinorgbio.2022.111769}}, volume = {{231}}, year = {{2022}}, }